Renewable Energy 85 (2016) 1116e1126

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Aqueous phase reforming (APR) of glycerol over platinum supported

on Al2O3 catalyst
A. Seretis, P. Tsiakaras*
Department of Mechanical Engineering, School of Engineering, University of Thessaly, Volos, Greece

a r t i c l e i n f o a b s t r a c t

Article history: The glycerol's APR reaction over 5% Pt/Al2O3 catalyst for H2 production in a batch reactor is investigated
Received 4 August 2014 in the present work. The effect of the operating parameters, such as the: i) reaction time, ii) operating
Received in revised form temperature, iii) glycerol concentration and iv) catalyst concentration on: a) the gaseous and liquid
22 July 2015
products selectivity, b) the glycerol's conversion and c) the H2 yield is investigated. Initially, the glycerol's
Accepted 24 July 2015
APR is studied at various temperature (200, 220, 240
C) and reaction time (30, 60, 120, 240 min), using
Available online xxx
1 wt.% or 10 wt.% glycerol solution and 0.5, 1, 2.5 g of 5% Pt/Al2O3 catalyst weight.
H2, CO, CH4 and CO2 are mainly detected in the gaseous phase and acetaldehyde, acetone, methanol,
Keywords:
Aqueous phase reforming
ethanol, 1-propanol, acetol, lactic acid, propylene glycol and ethylene glycol, in the liquid one. It is found
Hydrogenolysis that the optimum conditions were: 1 g of 5% Pt/Al2O3, 1 wt.% glycerol solution, 240
C and 4 h of reaction
Glycerol time. Under these conditions the total conversion of glycerol is found to be ~84% (~41% of gaseous and
Platinum ~39% of liquid products), H2 yield 14.1%, CH4 yield 3.1% and propylene glycol (the main liquid product)
Hydrogen production yield 25%. It is also found that, for 2.5 g of 5% Pt/Al2O3, 1 wt.% glycerol solution, 240
C and 4 h of reaction
time results the total conversion of glycerol is found to be ~68% (~45% of gaseous and 17% of liquid
products), H2 yield 16.5%, CH4 yield 7.4% and propylene glycol yield 8.1%. The increase of catalyst weight
leads mostly to gaseous products.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction introduced by Dumesic et al., in 2002 [10]. APR is a promising

Petroleum depletion and environmental contamination make
imperative the use of renewable resources such as biodiesel.
Biodiesel is produced from animal fats and vegetable oils and the
overall production-combustion process of which is considered as
carbon neutral [1]. It is known, the main by-product of biodiesel
production, (10 wt.% of the produced biodiesel), is glycerol [2]. It
is therefore essential to find effective and economical utilization
of glycerol. As reported in literature, glycerol as raw material for
the production of a variety of chemicals and fuels including H2,
which is the simplest and the most abundant element not free in
nature [3e7]. The H2 demand is continuously growing due to the
technological advancements in chemical and fuel cell industry
[8,9].
Among the catalytic reactions of oxygenated compounds (for
the conversion of biomass-derived hydrocarbons to more useful
products), the catalytic aqueous phase reforming (APR) was first
* Corresponding author.
E-mail address: tsiak@uth.gr (P. Tsiakaras).
process because: i) it can be carried out at relatively low T, ii) it is
not necessary to vaporize water and glycerol and iii) the undesir-
able decomposition reactions are minimized. Despite the fact that
glycerol's APR for H2 production in a fixed bed reactor (FBR) has
been extensively investigated [10e28], there are very few only in-
vestigations devoted to glycerol's APR for H2 production in a batch
reactor (BR).
Among the different catalytic systems, supported platinum
catalysts are the most extensively investigated for the glycerol's
APR in batch reactors. Meryemoglu et al. [29] studied experi-
mentally the APR of glycerol in a batch reactor (V ¼ 100 ml) at
three different catalysts: 5% Pt/Al2O3, 5% Pt/C and Raney Ni 2400.
The maximum hydrogen yield (1.6 mol H2/g catalyst) was
measured over Pt catalysts at reaction time t ¼ 2hr and reaction
temperature T ¼ 250
C. Ozgur et al. [21] studied glycerol's APR
in a batch reactor (Parr 4590 model) at temperature range
T ¼ 160e280
C using 2 g of a 1% Pt/Al2O3 catalyst in a 80 wt.%
glycerol solution. They found a hydrogen selectivity of 55% and a
total conversion of 24.5%, while the optimum reaction tempera-
ture was fixed at T ¼ 230
C. Barbelli et al. [30] studied the same

http://dx.doi.org/10.1016/j.renene.2015.07.068
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 A. Seretis, P. Tsiakaras / Renewable Energy 85 (2016) 1116e1126
Scheme 1. Aqueous Phase Hydrogenolysis (APH) of glycerol.
reaction using Pt catalysts supported on SiO2, a-Al2O3 and a-
Al2O3 modified with CeO2 and ZrO2 (Ce4Zr1a). The reaction
conditions were V ¼ 100 ml, T ¼ 200e250
C, t ¼ 2 h in 12 ml of
10 wt.% glycerol solution and 4.2 wt% catalyst concentration. The
PtCe4Zr1a turned out to be the most active (conversion to
gaseous products ¼ 29%), with the highest yield to H2 (20%).
Menezes et al. [31] investigated platinum catalysts supported on
Al2O3, CeO2, ZrO2 and MgO for glycerol's APR in a batch reactor
(Parr) at 225
C and autogenous pressure. The catalyst (100 mg)
was mixed with 100 mL of a 1 wt.% glycerol aqueous solution and
the reaction time was 3 h. Amongst all supports used, the catalyst
prepared on ZrO2 presented good activity (conversion ¼ 26%)
with high reaction rate (1.05 mol glycerol/gPt hr) and hydrogen
selectivity (62.7%). Ciftci et al. [32] studied experimentally the
APR of glycerol using carbon-supported Pt, Re, and PtRe catalysts.
The reaction conditions were V ¼ 120 ml, T ¼ 225
C, t ¼ 320 min
in 60 g of 10 wt.% glycerol solution and 75 mg catalyst amount.
The highest activity was observed for PtRe/C catalysts with Pt:Re
ratios of 1:2 and 1:5 (glycerol conversion ~45%).
Another important aspect, concerning the glycerol conversion is
its aqueous phase hydrogenolysis (APH) over a metal catalyst and
H2 atmosphere for the propylene glycol production [33e44].
However, glycerol hydrogenolysis to propylene glycol requires the
use of hydrogen as a reactant. An interesting alternative to avoid
the use of high molecular hydrogen pressures is the in situ gener-
ation of the required hydrogen in the reaction medium. Then,
expensive supply of external hydrogen is not necessary. A few
number of papers have investigated the possibility of coupling
glycerol APR with hydrogenolysis [45e49].
The purpose of this study is to find the appropriate reaction
conditions which favors i) the APR of glycerol for hydrogen pro-
duction and ii) the APH of glycerol with in situ generated hydrogen
for propylene glycol production. Finally, a complete study of the
reaction parameters (different reaction times, temperatures, re-
actants ratios, catalyst's weights), and a complete analysis of the
products (gaseous and liquids) is presented.
2. Experimental section
2.1. Materials
Glycerol (99.5%) was purchased from SigmaeAldrich and used
without further purification. The 5% Pt on alumina catalyst (%
H2O ¼ 2.68) was from Precious Metals Corporation PMC and used
as received in powder form. All other chemicals used in this study
were of either analytical or of reagent grade.
2.2. Catalytic tests
The APR experiments were carried out in a High Pressure
Reactor from Parr Instrument Company (Model 4563), with a
volume of 600 mL, operated in a batch mode. The selected range of
the studied reaction parameters is derived from a previous ther-
modynamic work [50] and from our preliminary experimental
tests.
The reactive mixture (250 ml) was an aqueous solution of 1 or
1117
10 wt.% of glycerol with 0.5, 1, 2.5 g of 5% Pt/Al2O3 catalyst (corre-
sponding to 25, 50, 125 mg of Pt, respectively). After loading the
reactive mixture, the reactor was purged with N2 and then pres-
surized to the desired initial reaction pressure with N2 (1 bar). The
catalytic tests were performed at 200, 220 and 240
C, resulting in
autogenous pressure of 16, 23.5 and 33.5 bar, respectively. The
stirring rate was set at 300 rpm. A gas and liquid sample were taken
for four different reaction times (30 min, 60 min, 120 min and
240 min). The liquid samples were periodically removed from the
reactor under the above mentioned reaction times. Especially, the
gas effluent cooled in a condenser in order to liquefy the con-
densable vapors and then a gas sample was taken with gas-syringe
of 5 ml.
2.3. Analysis of products
The analysis of the gaseous products was performed by a gas
chromatograph Shimadzu GC-14B equipped with a 1/8th inch
diameter, 15 ft long, 60/80 Carboxen-1000 column and a thermal
conductivity detector (TCD). Gas products were injected into GC
with gas-syringe of 5 ml. The products detected in the gas phase
were H2, CO, CH4 and CO2. The molar compositions of these
products were calculated without taking into account the
amount of steam. The nitrogen initially used was not taken into
account during calculations. Column temperature programme
was as follows: 10 min at 36
C, from 36 to 140
C with 10
C/min
heating rate and maintained at this temperature until the end of
analysis. The calibration was performed using standard gas
mixtures.
The analysis of liquid products was performed by a gas chro-
matograph Agilent 7890A equipped with a DB-WAX column
(30 m  0.53 mm  1.0 mm) and a flame ionization detector (FID).
Liquid products were injected into GC with a micro-volume syringe
of 10 ml. The compounds detected in the liquid phase were acetal-
dehyde, acetone, methanol, ethanol, 1-propanol, acetol, lactic acid,
propylene glycol, ethylene glycol and glycerol. Column temperature
programme was as follows: 7 min at 35
C, from 35 to 215
C with
5
C/min heating rate and maintained at this temperature until the
end of analysis. The carrier gas was helium with a flow rate 30 ml/
min. Acetonitrile was used as a solvent for the GC analysis. The
multiple point internal standard method was used for the quanti-
fication of the results. The accuracy of the measured values was
within 5% and the experiments could be reproduced with a relative
error of 10%.
Scheme 2. Hydrogenation reactions generating ethylene glycol, methanol, ethanol and
methane.
1118 A. Seretis, P. Tsiakaras / Renewable Energy 85 (2016) 1116e1126

3. Reactions-calculations NCH4
CH4 yieldð%Þ ¼  100
NC03 H8 O3  n
The APR process involves the following two main reactions [10]:
CeC cleavage leading to CO and H2, The propylene glycol yield is calculated as follows:

ðC3 H8 O3 Þl %3CO þ 4H2 0

DH25 0 C ¼ 338:025kJ=mol (1) Cpropyleneglycol
PGyieldð%Þ ¼  100
CC03 H8 O3
Wateregas shift reaction (WGS),

0 where
CO þ H2 O%CO2 þ H2 DH25 0 C ¼ 41:17kJ=mol (2)

Overall reaction of aqueous phase reforming (1) þ (2)
ðC3 H8 O3 Þl þ 3H2 O%3CO2 þ 7H2
And the Methanation reactions,
CO þ 3H2 %CH4 þ H2 O
CO2 þ 4H2 %CH4 þ 2H2 O
CC03 H8 O3 ; CC3 H8 O3 , initial and final glycerol concentration respec-
tively (g/lt)
0
DH25 0 C ¼ 214:515kJ=mol
NC03 H8 O3 , initial moles of glycerol
Cmethanol ; Cethanol ; C1propanol ; Cacetol ; Cpropyleneglycol ; Cethyleneglycol ,
(3)
concentrations of the main produced liquids (g/lt).
NH2 ; NCO2 ; NCH4 ; NCO , produced moles of H2, CO2, CH4 and CO
respectively
0
DH25 0 C ¼ 206:11kJ=mol (4) n ¼ 3, number of carbon atoms in the glycerol molecule
nH2 ¼ 7, number of hydrogen moles according to Eq. (3).
0
DH25 0 C ¼ 164:94kJ=mol (5)

The main liquid reactions are presented in the Scheme 1 [49]: 4. Results and discussion
The other liquid reactions are given in the Scheme 2 [51]:
The liquid products selectivity is expressed 4.1. Effect of reaction time and temperature

In Fig. 1, the selectivities of the gaseous products as a function of

Ci
Sli ð%Þ ¼  100
Cmethanol þ Cethanol þ C1propanol þ Cacetol þ Cpropyleneglycol þ Cethyleneglycol

The gaseous products selectivity is expressed as: the reaction time and temperature, in 1 wt.% glycerol solution and
500 mg of 5% Pt/Al2O3 catalyst, are depicted. It can be observed that,
g Ni at 200
C, the initial H2 selectivity is about 68.3% and decreases
Si ð%Þ ¼  100
NH2 þ NCO2 þ NCH4 þ NCO with the progress of the reaction reaching 59.1% after 4hr. At the
same time, the selectivity of CO2 increases from 29.6% to 38.8%
The total conversion (X) defined as: indicating that, apart from the reactions (1) and (2) shown above,
the reactions of methanation and hydrogenation take place leading
CC03 H8 O3  CC3 H8 O3 to the formation of intermediate products such as alcohols and
Xð%Þ ¼  100 alkanes [32]. Moreover, the selectivity of CO decreases from 0.2 to
CC03 H8 O3
0.11%, while the selectivity of CH4 slightly increases. The selectivity
The conversion to liquid products (XL) defined as: of CO is almost negligible (about 0.1%), as an intermediate product

Cmethanol þ Cethanol þ C1propanol þ Cacetol þ Cpropyleneglycol þ Cethyleneglycol

XL ð%Þ ¼  100
CC03 H8 O3

The conversion to gaseous products (XG) defined as: of reactions (1) and (2) and slightly decreases over time, mainly due
to the methanation reaction (4), which causes the increase of CH4
NCO2 þ NCH4 þ NCO selectivity. However, the selectivities of the gas mixture are in
XG ð%Þ ¼  100
n  NC03 H8 O3 agreement with previous studies [30,31]. The effect of temperature
on the selectivities of the gaseous products is also shown in Fig. 1.
The hydrogen yield is calculated as follows: Hydrogen selectivity decreases and CO2 selectivity increases as the
reaction temperature increases due to the higher conversions
NH2
H2 yieldð%Þ ¼  100 achieved at higher temperatures [10]. Furthermore, the CH4 and CO
NC03 H8 O3  nH2 selectivities increased at elevated temperatures.
In Fig. 2, the conversion to gaseous products, the hydrogen yield
The methane yield is calculated as follows:
 A. Seretis, P. Tsiakaras / Renewable Energy 85 (2016) 1116e1126 1119

Fig. 1. Gas products selectivities as a function of reaction time and temperature for the APR of 1 wt.% glycerol solution and 500 mg of 5% Pt/Al2O3 catalyst.

and the produced moles of hydrogen per gram of catalyst, are
presented as a function of the reaction time and temperature. It
should be noted that the glycerol conversion to gaseous products
increases with the increase of the temperature and the progress of
the reaction, tending to plateau with the higher value to be 13.4% at
T ¼ 240
C for 4 h reaction. In addition, with the increase in the
reaction temperature and time, the hydrogen yield and the
hydrogen moles produced per gram of platinum metal also in-
crease, as shown in Fig. 2b and c respectively. The maximum value
of H2 yield and the hydrogen moles produced per gram of platinum
metal reached 8.3% and 0.64 mol H2/g respectively in 4 h and
T ¼ 240
C. As reported in the introduction section, Meryemoglu
et al. [29] measured a maximum hydrogen yield (1.6 mol H2/g
catalyst) over Pt catalysts at reaction time t ¼ 2hr and reaction
temperature T ¼ 250
C, without any information about the pres-
sure of the system (crucial parameter for the hydrogen and
propylene glycol production) and the liquid products. The catalyst
performance (moles H2/g cat) in our case is lower due to the fact
that a significant amount of hydrogen is used for the hydrogenation
reactions (7e10).
Concerning the liquid phase, as mentioned before, the detected
products in order of increasing concentration are acetaldehyde,
acetone, 1-propanol, methanol, ethanol, ethylene glycol, propylene
glycol and acetol. The selectivities of the main liquid products
(acetol, propylene glycol, ethylene glycol, ethanol and methanol),
for the case of 1 wt.% glycerol solution and 500 mg of 5% Pt/Al2O3
catalyst, as a function of reaction time and temperature, are pre-
sented in Fig. 3. More specifically, the initial acetol selectivity is
about 67.4% at 200
C and increases with the progress of the re-
action reaching 80.8% after 2 h. Then, after 4 h of reaction, acetol
selectivity decreases to 76.1%. At 220
C the acetol selectivity in-
creases in the first hour of reaction, then decreases and finally at

Fig. 2. a)Conversion to gaseous products, b) H2 yield and c) produced H2 moles per gram of platinum catalyst as a function of reaction time and temperature for the APR of 1 wt.%
glycerol solution and 500 mg of 5% Pt/Al2O3 catalyst.
1120 A. Seretis, P. Tsiakaras / Renewable Energy 85 (2016) 1116e1126
Fig. 3. Liquid products selectivities as a function of reaction time and temperature for the APR of 1 wt.% glycerol solution and 500 mg of 5% Pt/Al2O3 catalyst.
240
C the acetol selectivity decreases with reaction time.
As well know from literature, also in the present case (batch
reactor), the reaction time plays a major role on products' distri-
bution and thus during short reaction times, acetol was the major
product whereas for longer reaction times, the selectivity to PG
increased [34,40,41,45,52]. It was suggested that the first step of
glycerol hydrogenolysis requires acid sites for dehydration to acetol
followed by metal catalyzed hydrogenation to propylene glycol as
shown in Scheme 1 [49]. Then in longer times, the formation of
ethylene glycol (C2H6O2) due to severe hydrogenation would occur
as shown in reaction (8). In addition, it is important to note that the
DB-WAX column has proved to be more sensitive to ethanol
detection than ethylene glycol. As a result, at lower reaction times
Fig. 4. Conversion to gaseous products, conversion to liquids products and total con-
version as a function of reaction time for three different temperatures for the APR of
1 wt.% glycerol solution and 500 mg of 5% Pt/Al2O3 catalyst.
and temperatures (small conversions) where the products' con-
centrations are limited, ethanol can be detected but not EG. As the
reaction proceeds the quantity of the products PG, EG increases
more than that of ethanol which means that ethanol selectivity
decreases. But, the crucial is that the quantity of ethanol increases.
Regarding the methanol, as an intermediate product its quantity
depends on the kinetics of the reactions (8) and (10). Anyway, the
selectivity of methanol decreases as reaction proceeds and as the
reaction temperature increases as shown in Fig. 3.
The conversion to gaseous products, conversion to liquids
products and total conversion as a function of reaction time for
three different temperatures for the case of 1 wt.% of glycerol so-
lution and 500 mg of 5% Pt/Al2O3 catalyst are schematically shown
in Fig. 4. As it can be seem, the conversion increases with reaction
time, reaching for both gases and liquids a plateau at ~2 h of re-
action time as reported in other works [21,49]. It is observed that, at
shorter reaction times, the conversion to gaseous products is higher
than that of liquids. However, as reaction proceeds, the conversion
to liquid products becomes higher. Higher conversions were ach-
ieved at higher temperatures for both the gas and liquid phase.
Similarly Rode et al. [52] presented that the total glycerol conver-
sion increases as the temperature increases, with external
hydrogen addition and copper catalyst. Also other works using
nickel catalysts presented the same trend [53,54] The highest
conversion value (42%) was achieved at 240
C for 4 h of reaction
time. The mass balances of 1 wt.% glycerol solution and 500 mg of
5% Pt/Al2O3 catalyst at three different temperatures, are given in
Table 1. It is confirmed that the sum of the measured values of the
remaining glycerol and the detected gas and liquid products are
close to 10 g/lt, which is the initial glycerol concentration.
4.2. Effect of catalyst concentration
In Fig. 5, are depicted the selectivities of gaseous products as a
function of reaction time for three different catalyst concentrations
(0.5, 1, 2.5 g) and 1wt.% glycerol solution at T ¼ 240
C. It can be
 A. Seretis, P. Tsiakaras / Renewable Energy 85 (2016) 1116e1126 1121

Table 1
Mass balances for the APR of 1wt% glycerol solution (10 gr/lt) and 500 mg of 5% Pt/Al2O3 catalyst at three different temperatures.

Mass balances

Reaction time (hr) Glycerol remaining Liquids products Gaseous products Sum (gr/lt)


T ¼ 200 C 0.5 9,525491 0,050137 0,336166 9,911795
1 8,948509 0,105154 0,316925 9,370587
2 8,300147 0,402066 0,394442 9,096654
4 8,304518 0,860365 0,377650 9,542534
T ¼ 220
C 0.5 9,390303 0,114347 0,470896 9,975546
1 8,579175 0,754989 0,651091 9,985254
2 7,227295 1,511080 0,694319 9,432694
4 7,386517 1,788151 0,734959 9,909627
T ¼ 240
C 0.5 8,984739 0,263925 0,641291 9,889955
1 7,768047 1,333756 0,827162 9,928965
2 6,514043 2,397541 0,956507 9,868091
4 5,790563 2,648426 1,344851 9,783841

distinguished that, hydrogen selectivity decreases with time, as
reported before. Moreover, it is observed that by increasing the
catalyst concentration (from 0.5 to 1 g), the selectivity of hydrogen
decreases, whereas a further increase of catalyst weight (from 1 to
2.5 g) further enhances hydrogen selectivity. The selectivity of
carbon dioxide presents the inverse behaviour. In addition,
methane selectivity increases with both the increase of the catalyst
concentration and the reaction evolution. Finally, the selectivity of
carbon monoxide follows the inverse of the methane selectivity
behavior.
In Fig. 6, it is observed that by increasing the catalyst concen-
tration (from 0.5 to 1 g) the conversion to gaseous products greatly
increases from 13.4 to 40.34% (almost 200% of increase). A further
increase of catalyst weight (from 1 to 2.5 g) increases mainly the
conversion to gaseous products from 40 to 45%. Yadav et al. [40]
studied the effect of catalyst loading in the range of 0.2 g (2% w/
w of glycerol) to 0.65 g (6.5% w/w of glycerol). The conversion was
linearly increased for catalyst loading up to 5% due to the increase
in the number of active sites in the catalyst However, they resulting
that beyond a catalyst loading of 5% w/w, there was no increase in
conversion suggesting that more number of active sites were
available.
Similarly, the yields of H2 and CH4 are also increased with the
increase of the catalyst weight (from 0.5 g / 1 g / 2.5 g) from 8.3
to 14.1 to 16.5% and from 0.63 to 3.13 to 7.4% respectively. It is worth
noting that the catalyst performance (moles H2/g cat) is decreased

Fig. 5. Gas products selectivities as a function of reaction time for three different catalyst concentrations (0.5e1e2.5 g of 5% Pt/Al2O3) for the APR of 1 wt.% glycerol solution at
T ¼ 240
C.
1122 A. Seretis, P. Tsiakaras / Renewable Energy 85 (2016) 1116e1126

Fig. 6. Conversion to gaseous products, H2 yield, CH4 yield, produced H2 moles per gram of platinum catalyst and reforming H2/CO2 ratio as a function of reaction time for three
different catalyst concentrations (0.5e1e2.5 g of 5% Pt/Al2O3) for the APR of 1 wt.% glycerol solution at T ¼ 240
C.

Fig. 7. a) Liquid products selectivities and b) Conversion to gaseous products, conversion to liquids products and total conversion as a function of reaction time for three different
catalyst concentrations (0.5e1e2.5 g of 5% Pt/Al2O3) for the APR of 1 wt.% glycerol solution at T ¼ 240
C.
 A. Seretis, P. Tsiakaras / Renewable Energy 85 (2016) 1116e1126 1123

Table 2
Mass balances for the APR of 1wt% glycerol solution (10 gr/lt) at 240
C for three different catalyst concentrations.

Mass balances

Reaction time (hr) Glycerol remaining Liquids products Gaseous products Sum (gr/lt)

0.5 gr of 5%Pt/Al2O3 0.5 8,984739 0,263925 0,641291 9,889955

1 7,768047 1,333756 0,827162 9,928965
2 6,514043 2,397541 0,956507 9,868091
4 5,790563 2,648426 1,344851 9,783841
1 gr of 5%Pt/Al2O3 0.5 7,209585 0,509483 1,175530 8,894599
1 6,246235 1,073267 2,124607 9,444109
2 4,409841 2,260098 3,286716 9,956654
4 1,611854 3,864146 4,034686 9,510685
2.5 gr of 5%Pt/Al2O3 0.5 7,939060 0,315549 1,513735 9,768343
1 6,286791 0,392910 2,287619 8,967321
2 5,343584 0,879085 3,628626 9,851295
4 3,140831 1,688446 4,500856 9,330133

from 0.64 to 0.54% as catalyst mass increases (from 0.5 to 1 g),
whereas a further increase (1e2.5 g) causes a great decrease from
0.54 to 0.25%.
The selectivities of the main liquid products (acetol, propylene
glycol, ethylene glycol, ethanol and methanol), for 1 wt.% glycerol
solution at 240
C as a function of reaction time for the three
different catalyst weights (0.5, 1 and 2.5 g) of 5% Pt/Al2O3 catalyst, are
shown in Fig. 7a. More specifically, the initial selectivity in acetol is
about 85% for the first case (0.5 g) and decreases as the reaction is
progressing, reaching, after 4hr, 53.7%. For the second (1 g) and third
case (2.5 g), the acetol selectivity is decreased from 78.3 to 14.66%
and from 75.8% to 18.4% respectively. The propylene glycol selectivity
is increased with reaction time as mentioned before reaching 35.75%
for the first case, 64.93% for the second case and 48.01% for the third
case. At this point it can be concluded that the production of the
main liquid product (propylene glycol) is higher when the catalyst
quantity is 1 g. Maglinao et al. [47] similarly observed that increasing
the concentration of nickel catalyst to above 6.4 wt.% would not
significantly improve the yield of propylene glycol under the studied
conditions. The propylene glycol yield reaches 25% and this PG
production requires hydrogen consumption. This explains the why
the reforming ratio of hydrogen to carbon dioxide was lower for the
case of 1 g of 5% Pt/Al2O3. In a similar work under N2 pressure, the
PtSn0.2 catalyst showed 55% of glycerol conversion to liquid with

Fig. 8. Gas products selectivities as a function of reaction time for the APR of 1 wt.% and 10 wt.% glycerol solution with 500 mg of 5% Pt/Al2O3 catalyst at T ¼ 240
C.
1124 A. Seretis, P. Tsiakaras / Renewable Energy 85 (2016) 1116e1126

Fig. 9. a)Conversion to gaseous products, b) H2 yield and c) produced H2 moles per gram of platinum catalyst as a function of reaction time for the APR of 1 wt.% and 10 wt.% glycerol
solution with 500 mg of 5% Pt/Al2O3 catalyst at T ¼ 240
C.

59% selectivity to propylene glycol leading to the highest yield to
propylene glycol 32% [48].
The conversion to gaseous products, to liquids products and
total conversion as a function of the reaction time, for three
different catalyst weights (0.5, 1, 2.5 g of 5% Pt/Al2O3) and 1 wt.%
glycerol solution at 240
C are shown in Fig. 7b. It can be seen that,
by increasing the catalyst concentration (from 0.5 to 1 g), the total
conversion increases (for constant glycerol quantity) reaching 84%,
whereas a further increase (from 1 to 2.5 g) favors only the
conversion to gaseous products and inhibits the conversion to
liquid products. The value of the conversion is high enough
compared with other similar works [21,30e32,45,46,48,49] Finally,
the mass balances and 1 wt.% glycerol solution at 240
C for three
different catalyst weights are given in Table 2. It is confirmed that
the sum of the measured values of the remaining glycerol and the
detected gas and liquid products are very close to 10 g/lt, which is
the initial glycerol concentration.

Fig. 10. a) Liquid products selectivities and b) Conversion to gaseous products, conversion to liquids products and total conversion as a function of reaction time for the APR of
1 wt.% and 10 wt.% glycerol solution with 500 mg of 5% Pt/Al2O3 catalyst at T ¼ 240
C.
 A. Seretis, P. Tsiakaras / Renewable Energy 85 (2016) 1116e1126
Table 3
Mass balances for the APR of 1 (10gr/lt) and 10wt% glycerol solution (100 gr/lt) and 500 mg of 5%Pt/Al2O3 catalyst at 240
C.
Mass balances
Reaction time (hr) Glycerol remaining
Initial glycerol concentration (10 gr/lt) 0.5 8,984739
1 7,768047
2 6,514043
4 5,790563
Initial glycerol concentration (100 gr/lt) 1 91,25585
2 88,09120
4 86,57104
4.3. Effect of glycerol concentration
The gas products selectivities as a function of the reaction time,
for 1 wt.% and 10 wt.% glycerol solution with 500 mg of 5% Pt/Al2O3
catalyst at T ¼ 240
C, are reported in Fig. 8. It is obvious that the
increase of glycerol concentration (for constant catalyst quantity)
does not significantly affect the products selectivity. Particularly,
the hydrogen selectivity values are very close and there is a little
difference in the carbon monoxide ones.
The conversion to gaseous products, the H2 yield and the pro-
duced H2 moles per gram of platinum catalyst as a function of the
reaction time, for 1 wt.% and 10 wt.% glycerol solution with 500 mg
of 5% Pt/Al2O3 catalyst at T ¼ 240
C, are shown in Fig. 9. It is
observed that the increase of glycerol concentration greatly reduces
the conversion of glycerol and the yield of hydrogen. This is prob-
ably due to the reduction of the catalyst to glycerol ratio. For
example, the value of the catalyst to glycerol ratio is 0.001 (g Pt/g
gly) for 10 wt.% glycerol solution and 500 mg of 5% Pt/Al2O3 catalyst
instead of 0.01 (g Pt/g gly) for the case of APR of 1 wt.% glycerol
solution and 500 mg of 5% Pt/Al2O3 catalyst. Nevertheless, the
catalyst performance (moles H2/g cat) is not affected. This also
means that the catalyst amount cannot reform the additional
quantity of glycerol.
The selectivities of the main liquid products (acetol, propylene
glycol, ethylene glycol, ethanol and methanol), as a function of
reaction time, for 1 wt.% and 10 wt.% glycerol solution with 500 mg
of 5% Pt/Al2O3 catalyst at T ¼ 240
C, are presented in Fig. 10a. As it
can be seen, in this case acetol is the main liquid product and the
second one is propylene glycol. . It is also seen that, the final acetol
selectivity is 53.7% for the 1 wt.% glycerol solution, This value is very
close to 53.8% for that measured over 10 wt.% of glycerol solution.
Additionally, the final propylene glycol selectivity is 35.75 and
28.34% respectively. The conversion to gaseous products, conver-
sion to liquids products and total conversion as a function of the
reaction time, for 1 wt.% and 10 wt.% glycerol solution with 500 mg
of 5% Pt/Al2O3 catalyst at T ¼ 240
C, are shown in Fig. 10b. As seen,
by increasing the glycerol concentration (for constant catalyst
quantity) the total conversion and the conversion to liquids prod-
ucts are both decreased from 42 to 13.4% and from 26.4 to 9.13%
respectively, whereas the conversion to gaseous products is greatly
reduced from 13.4 to 1.46%. Therefore, the conversion of glycerol
decreased with increasing the concentration of glycerol in the re-
action media, but the selectivity of propylene glycol was almost
unchanged, implying that the conversion of glycerol is simply
associated with the number of active sites, in accordance with
previous finding over Co/MgO catalyst [55]. It is assumed that the
catalyst concentration is very low and that's why the conversion
values are very low. The mass balances for the APR of two different
glycerol concentrations with 500 mg of 5% Pt/Al2O3 catalyst at
240
C are given in Table 3. It is confirmed that the sum of the
measured values of the remaining glycerol and the detected gas
and liquid products are very close to 100 g/lt, which is the initial
1125
Liquids products Gaseous products Sum (gr/lt)
0,263925 0,641291 9,889955
1,333756 0,827162 9,928965
2,397541 0,956507 9,868091
2,648426 1,344851 9,783841
5,753964 0,735913 97,74572
9,362134 0,937073 98,39041
9,314766 1,464379 97,35018
glycerol concentration for the second case.
5. Conclusions
With the increasing production of biodiesel, glycerol has
become a potential renewable source for hydrogen production.
Aqueous phase reforming offers many advantages, from a technical
and economic point of view, since it is possible to produce in a
single stage reactor (batch reactor) hydrogen gas, with negligible
amounts of CO, appropriate for fuel cell applications as well as it is
not necessary to vaporize water and glycerol in reforming process.
In this work the experimental investigation of glycerol's APR
and hydrogenolysis over platinum catalyst supported on Al2O3 has
been performed. It was found that the operating parameters greatly
affect the selectivity and the yield of the useful products and the
glycerol conversion. It should be pointed out that the selectivity to
hydrogen decreased at elevated temperatures and with the reac-
tion evolution, which indicates that not only the APR, but other
reactions occur contemporaneously (mainly methanation and
hydrogenolysis). The glycerol conversion increases with the in-
crease of the temperature and the reaction evolution, reaching a
plateau. It is observed that by increasing the catalyst concentration
(0.5e1 g), the total conversion increases (for constant glycerol
quantity), whereas a further increase (1e2.5 g) favors only the
conversion to gaseous products. Moreover, increasing the glycerol
concentration (for constant catalyst quantity) does not affect the
products selectivity, but greatly reduces the glycerol conversion.
This is probably due to the reduction of the catalyst to glycerol ratio.
Nevertheless, the catalyst performance (moles H2/g cat) is not
affected.
Acknowledgements
This research has been co-financed by the European Union
(European Social Fund e ESF) and Greek national funds through the
Operational Program “Education and Lifelong Learning” of the
National Strategic Reference Framework (NSRF) e Research Fund-
ing Program: THALES: Investing in knowledge society through the
European Social Fund, grant number MIS 379333.
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